CN107163080B - 刺激响应三苯乙烯类光致变色材料及其合成方法与应用 - Google Patents
刺激响应三苯乙烯类光致变色材料及其合成方法与应用 Download PDFInfo
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Abstract
本发明公开了一种刺激响应三苯乙烯类光致变色材料及其合成方法与应用,为含有刺激响应官能团的三苯乙烯类材料。本发明的合成方法工艺简单,容易纯化,具有良好的变色性能和可擦写性,适合作为光控开关、记忆存储材料等。此外,通过官能团调控本发明中的化合物还可以产生刺激响应特性,适用应用于化学生物检测,生物成像以及防伪等领域。
Description
技术领域
本发明涉及有机发光材料领域,特别是一种刺激响应三苯乙烯类光致变色材料及其合成方法,以及在光控材料、光信息存储的应用。
背景技术
光致变色材料是指在光的作用下可以发生可逆或不可逆的物理或化学变化,并且在可见光吸收上发生变化的材料。(Diirr,H.,Bouas-Lament H.Pure and AppliedChemistry,2001)随着近几十年来基础科学理论和分析检测技术的发展,人们已经能够通过使用光致变色材料实现分子尺度上各种物理以及化学性质的精确调控。光致变色材料在安全防伪、光学掩膜、光开关分子器件、生物成像以及光记忆存储等领域展现出了十分巨大的研究和应用价值。
光致变色现象在无机和有机化合物中均可发生,有机光致变色化合物因其结构确定易修饰、抗疲劳性好等特点逐渐成为光致变色材料的主要研究对象。(Minkin VI.Chemical reviews,2004)有机光致变色材料主要有以下几种:螺吡喃类、螺噁嗪类、苯并吡喃类、偶氮类、俘精酸酐类、三苯甲烷类、二芳基乙烯类化合物。然而传统有机光致变色材料大多存在设计合成复杂、材料成本高、易氧化以及循环次数差等问题。然而二芳基乙烯类化合物,因其结构简单易修饰,具有优异的化学和物理稳定性、良好的抗疲劳性等优点,显示了其巨大的市场潜力,近年来逐渐成为研究的热点方向。刺激响应光致变色材料,是指在外界刺激因素包括光、温度、pH、离子强度、电场和磁场等刺激下材料本身增强或减弱变色特性的一类材料。刺激响应作用的存在使得材料呈现多重逻辑门效应,在单分子开关、生物探针等方面具有更加广阔的应用前景。Diana Dulic等人通过官能团修饰,合成了一系列变色强度具有温度依赖的刺激响应的二芳基乙烯类光致变色材料。(Diana D.AdvancedMaterials,2007)
三苯乙烯类光致变色材料的设计合成更加简洁高效,并且可以通过官能团调控,得到具有多种刺激响应的光致变色材料,可以用于光控材料、光信息存储、化学生物检测、生物成像以及防伪等多个领域。此外,温和的合成条件,低廉的原料价格以及高产率也将赋予该类材料更大的市场潜力。
发明内容
本发明的目的是提供一种刺激响应三苯乙烯类光致变色材料,其拥有刺激快速响应的、具有良好可擦写性等优点。
本发明的另一个目的是为上述刺激响应三苯乙烯类光致变色材料提供多种合成方法,这些方法工艺简单,产率高,易于纯化,并可通过引入不同官能团进而调节终产物的变色条件、变色波长等性能。
本发明的第三个目的是将此类刺激响应三苯乙烯类光致变色材料应用于光控材料、光信息存储、生物成像、防伪等领域。
为实现上述目的,本发明提供一种刺激响应三苯乙烯类光致变色材料,其特征在于分子结构通式
如通式(1)所示:
通式(1):
其中,R0为刺激响应基团,选自硝基、羧基、氨基、醛基、氰基、硼酸酯、硼酸频哪醇酯、含膦或含硼芳香环或其芳香杂环取代基;R1与R2相同或不同,R1和R2选自烷基、卤素、硝基、羧基、氨基、醛基、氰基、硼酸、硼酸频哪醇酯、芳香环或芳香杂环取代基。
上述刺激响应三苯乙烯类光致变色材料的合成方法,其特征在于包括:方法(1)将含膦或含硼芳香环或其芳香杂环取代基的化合物与一端、两端或三端含有卤素的三苯乙烯衍生物反应得到目标产物;方法(2)将二苯酮衍生物与含有磷酸二乙酯基的苯系物反应通过维悌希反应得到目标产物;方法(3)将卤代苯系物与一端、两端或三端含有炔基的三苯乙烯衍生物通过薗头偶合反应得到目标产物;方法(4)将以上方法(1)、(2)或(3)得到的目标产物,进一步通过氧化、水解、pH调节或聚集态调控得到相应的目标产物。
上述刺激响应三苯乙烯类光致变色材料在制备光控材料、光信息存储产品、化学生物检测产品、生物成像产品或防伪产品上的应用。
本发明的合成方法工艺简单,容易纯化,所合成的光致变色材料具有响应速度快以及良好的可擦写性,适用于光控材料、光信息存储等领域。此外,本发明中含有膦的光致变色材料对氧气、金属离子等具有特异性响应,含有羧基的光致变色材料对碱性、潮湿环境等具有特异性响应,尤其适用于化学生物检测、生物成像以及防伪等领域。
为了能更进一步阐述本发明的特征及技术内容,请参阅以下有关本发明的附图,但附图仅为提供参考与说明,并非用于对本发明加以限制。
附图说明
图1、图2分别是本发明实施例2产物的溶液光致变色前后对比图片、紫外吸收光谱对比图;
图3、图4分别是本发明实施例4产物的粉末光致变色前后对比图片、紫外吸收光谱对比图;
图5是本发明实施例5产物对碱、水刺激响应的光致变色前后对比图片。
具体实施方式
本发明的刺激响应三苯乙烯类光致变色材料其分子通式如通式(1)所示:
通式(1):
其中,R0为刺激响应基团,可以选自硝基、羧基、氨基、醛基、氰基、硼酸酯、硼酸频哪醇酯、含膦或含硼芳香环或其芳香杂环取代基。
其中R0为含膦或含硼芳香环基团或其芳香杂环取代基时,优选自以下结构:
其结构中R3可以与R4相同,也可以不同,R3和R4可以为氢、烷基、卤素、烷氧基、硝基、羧基、氨基、醛基、氰基、苯基、萘基、蒽基、咔唑衍生物基、二苯胺衍生物基或吩噻嗪衍生物基。
通式(1)中R1可以与R2相同,也可以不同,R1和R2可以为烷基、卤素、硝基、羧基、氨基、醛基、氰基、硼酸、硼酸频哪醇酯、芳香环或芳香杂环取代基。其中R1和R2为芳香环或芳香杂环取代基时,优选自以下结构:
其结构中R5可以与R6相同,也可以不同,R5和R6可以为氢、烷基、卤素、硝基、羧基、氨基、醛基、氰基、苯基、萘基、蒽基、咔唑基、二苯胺基或吩噻嗪基。
上述刺激响应三苯乙烯类光致变色材料的合成方法,包括:
方法(1)将含膦或含硼芳香环或其芳香杂环取代基的化合物与一端、两端或三端含有卤素的三苯乙烯衍生物反应得到目标产物。优选的,方法(1)是提供含膦或含硼芳香环或其芳香杂环取代基的化合物与含有卤素的三苯乙烯衍生物,在甲苯溶液中,在钯催化剂作用下,加热回流得到目标产物。
方法(2)将二苯酮衍生物与含有磷酸二乙酯基的苯系物反应通过维悌希反应得到目标产物。优选的,方法(2)是提供二苯酮衍生物与含有磷酸二乙酯基的苯系物在四氢呋喃溶液中,在叔丁醇钾作用下通过维悌希反应得到目标产物。
方法(3)将卤代苯系物与一端、两端或三端含有炔基的三苯乙烯衍生物通过薗头偶合反应得到目标产物。优选的,方法(3)是提供卤代苯系物与一端、两端或三端含有磷酸二乙酯基的三苯乙烯衍生物在四氢呋喃溶液中,在三乙胺和钯催化剂作用下通过薗头偶合反应得到目标产物。
方法(4)是将以上方法(1)、(2)或(3)得到的目标产物,进一步通过氧化、水解、pH调节或聚集态调控得到相应的目标产物。
以下通过具体的实施例子对本发明作进一步的阐述,但本发明并不限于此特定例子。
实施例1
(1)中间体【4-碘苯磷酸二乙酯】的合成
250ml单口烧瓶中加入2.95克4-碘溴苄(0.01mol)和6.85ml亚磷酸三乙酯(0.04mol),反应液开始为悬浮液,在磁力搅拌器上,使用金属加热套加热至190℃回流,得澄清溶液,回流6小时后,冷至室温,减压蒸掉过量的亚磷酸三乙酯(油浴温度不高于120℃),残留溶液冷却后得到固体,用正己烷洗涤,过滤,干燥,得黄白色固体3.20克,产率90.40%。
(2)中间体【1,1-二(4-氯苯)-2-(4-碘苯)乙烯】的合成
250mL三口瓶中加入4-碘溴苄(1.77g,5.00mmol),加入适量THF,在氮气环境中加入t-BuOK(1.68g,15.00mmol)。搅拌半小时后加入4,4’-二氯二苯甲酮(2.00g,8mmol),反应12h。之后将反应液冷却,加入二氯甲烷和水萃取,用二氯甲烷萃取3次,再用水洗3次。将有机层用无水硫酸钠干燥,在旋转蒸发仪中旋干。然后利用硅胶柱层析的方法进行提纯,淋洗液为体积比1:3的二氯甲烷和正己烷的混合溶液。得白色固体1.76g,产率78.22%。
(3)目标产物的合成
将中间体A(1.00g,2.22mmol)溶于甲苯中,加入2mL三乙胺。加入二苯基膦(0.59g,3.17mmol)。升高温度至溶剂回流,加入四(三苯基膦)钯0.05g作为催化剂,搅拌回流36小时后将反应液冷却,抽滤,滤液用旋转蒸发仪蒸干。用硅胶柱层析的方法进行提纯,淋洗液为体积比1:3的二氯甲烷和正己烷的混合溶液。得纯产物0.70g,产率62%。1H NMR(400MHz,CDCl3,298K,relative to Me4Si)δ=6.92(s,1H),6.98–7.00(m,2H),7.09-7.12(m,4H),7.20(d,8.7Hz,2H),7.27-7.34(m,14H).
实施例2
将实施例1所得的产物(0.38g,0.75mmol)加入圆底烧瓶中,加入20mL四氢呋喃中溶解。加入6mL过氧化氢水溶液(30%),搅拌5小时后,在反应液中加入二氯甲烷、水各50mL后分液。将二氯甲烷层用旋转蒸发仪旋干,得白色粉末。将白色粉末用二氯甲烷/正己烷重结晶,得到白色固体0.34g,产率86.28%。1H NMR(600MHz,CDCl3,298K,relative toMe4Si):δ=6.9599(s,1H),7.10-7.14(m,4H),7.24(d,8.6Hz,2H),7.31-7.33(m,4H),7.45-7.50(m,6H),7.55-7.58(m,2H),7.65-7.68(m,4H).
本实施例产物的溶液光致变色前后对比如图1所示,紫外吸收光谱对比如图2所示。
实施例3
(1)中间体【4-氰基苯磷酸二乙酯】的合成
参照实施例1的步骤(1)利用4-氰基溴苄代替4-碘溴苄合成4-氰基苯磷酸二乙酯,产率89.38%。(2)目标产物的合成
参照实施例1的步骤(2)利用4-氰基苯磷酸二乙酯代替4-碘苯磷酸二乙酯合成目标产物,产率为76.46%。1H NMR(500MHz,CDCl3,298K,relative to Me4Si):δ=6.92(s,1H),7.07-7.11(m,4H),7.22(d,8.6Hz,2H),7.30-7.34(m,4H),7.44(d,8.4Hz,2H).
实施例4
参照实施例3的步骤(2)利用4,4’-二氟二苯甲酮代替4,4’-二氯二苯甲酮,合成目标产物,产率为72.77%。1H NMR(500MHz,CDCl3,298K,relative to Me4Si):δ=6.87(s,1H),7.02-7.13(m,8H),7.26-7.29(m,2H),7.55-7.58(m,2H),7.43(d,8.35Hz,2H).
本实施例产物的粉末光致变色前后对比如图3所示,紫外吸收光谱对比如图4所示。
实施例5
将实施例3所得的目标产物(0.70g,2mmol)溶于50mL乙二醇中,加入氢氧化钾(0.112g,10mmol)。升高温度至溶剂回流,搅拌回流72小时后将反应液冷却,用二氯甲烷洗涤三次后加入稀盐酸中,抽滤,滤饼用二氯甲烷/正己烷重结晶,真空干燥,得浅白色产物0.41g,产率55.55%。1H NMR(500MHz,CDCl3,298K,relative to Me4Si):δ=6.97(s,1H),7.09-7.12(m,4H),7.24(d,8.6Hz,2H),7.30-7.33(m,4H),7.89(d,8.4Hz,2H).
本实施例产物对碱、水刺激响应的光致变色前后对比如图5所示。
实施例6
(1)中间体【1,1-二(4-溴苯)-2-(4-苄腈)乙烯】的合成
参照实施例3的步骤(2)利用4,4’-二溴二苯甲酮代替4,4’-二氯二苯甲酮合成1,1-二(4-溴苯)-2-(4-苄腈)乙烯,产率为75.31%。
(2)目标产物的合成
参照实施例5的步骤利用中间体1,1-二(4-溴苯)-2-(4-苄腈)乙烯合成目标产物,产率为61.00%。1H NMR(500MHz,DMSO-d6,298K,relative to Me4Si):δ=7.08(d,8.3Hz,2H),7.12(d,8.4Hz,2H),7.20(s,1H),7.24(d,8.6Hz,2H),7.55(d,8.6Hz,2H),7.59(d,8.3Hz,1H),7.72(d,8.3Hz,2H),12.86(s,1H).
实施例1-6中终产物在固体的最大荧光发射波长、最大变色紫外吸收波长以及特异性刺激响应条件见表1。
表1:
注:固体的发射光谱由Shimadzu RF-5301PC荧光分光光度计测量;紫外吸收光谱由Hitachi U-3900分光光度计测量。
综上所述,本发明中的光致变色材料具有良好的变色性能和可擦写性,适合作为光控开关、记忆存储材料等。此外,通过官能团调控本发明中的化合物还可以产生刺激响应特性,如含膦化合物对发光材料还对氧气、金属离子等具有特异性响应,羧酸化合物对碱性和水等具有特异性响应等,适用应用于化学生物检测,生物成像以及防伪等领域。以上所述,本领域的普通技术人员可以根据本发明的技术方案和技术构思作出其它各种相应的改变和变形,而所有这些改变和变形都应属于本发明权利要求的保护范围。
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